Abstract--The formation of hematite from amorphous Fe(III)hydroxide in aqueous systems at pH 6 and 70~ both with and without oxalate, was followed by kinetic measurements, electron microscopy, i.r. spectroscopy and thermal analysis.In the absence of oxalate, small amorphous particles coalesce into aggregates which eventually become single crystals of hematite. When oxalate is present, crystal growth is much faster and does not proceed through the intermediate stage of aggregation. Aggregates, when formed, consist of groups of single crystals. It is suggested that oxalate accelerates the nucleation of hematite crystals by acting as a template, the Fe-Fe distance in Fe oxalate ions being similar to that in hematite.
Soil wettability affects hydrological processes like infiltration, percolation, preferential flow, and surface runoff. Wettability is related to the soil‐water contact angle, which in turn depends on the solid surface free energy. Little is known, however, about contact angles and their dependence on soil water potential. The main objective of this study was therefore to investigate the dynamics of contact angle due to variation of the water potential. Aggregate fractions of 2‐ to 4‐, 1‐ to 2‐, and <1‐mm diameter and corresponding homogenized material of a subcritical water repellent Orthic Luvisol were studied at water potentials of −1000, −154, −30, and −0.14 MPa. Wettability was assessed in terms of the advancing contact angle by the capillary rise method (CRM). Additionally, we calculated the surface free energy. Results showed, that the contact angle increased as water potential increased to a specific level. It was found for several soil samples, that above this water potential level, the contact angle decreased again. The change of contact angle due to variation of water potential reached nearly 90° for one sample. Contact angles of homogenized fractions were slightly larger than those measured for the aggregate surfaces. Surface free energy was consistently between 55 and 65 mJ m−2 with relative contributions of the dispersion and polar components to surface free energy of approximately 1/3 and 2/3, respectively. We conclude, that the assessment and physical description of the specific water potential for which a surface becomes wettable is a key factor for a better understanding of soil wetting.
The protective impact of aggregation on microbial degradation through separation has been described frequently, especially for biotically formed aggregates. However, to date little information exists on the effects of organic‐matter (OM) quantity and OM quality on physical protection, i.e., reduced degradability by microorganisms caused by physical factors. In the present paper, we hypothesize that soil wettability, which is significantly influenced by OM, may act as a key factor for OM stabilization as it controls the microbial accessibility for water, nutrients, and oxygen in three‐phase systems like soil. Based on this hypothesis, the first objective is to evaluate new findings on the organization of organo‐mineral complexes at the nanoscale as one of the processes creating water‐repellent coatings on mineral surfaces. The second objective is to quantify the degree of alteration of coated surfaces with regard to water repellence. We introduce a recently developed trial that combines FTIR spectra with contact‐angle data as the link between chemical composition of OM and the physical wetting behavior of soil particles. In addition to characterizing the wetting properties of OM coatings, we discuss the implications of water‐repellent surfaces for different physical protection mechanisms of OM. For typical minerals, the OM loading on mineral surfaces is patchy, whereas OM forms nanoscaled micro‐aggregates together with metal oxides and hydroxides and with layered clay minerals. Such small aggregates may efficiently stabilize OM against microbial decomposition. However, despite the patchy structure of OM coating, we observed a relation between the chemical composition of OM and wettability. A higher hydrophobicity of the OM appears to stabilize the organic C in soil, either caused by a specific reduced biodegradability of OM or indirectly caused by increased aggregate stability. In partly saturated nonaggregated soil, the specific distribution of the pore water appears to further affect the mineralization of OM as a function of wettability. We conclude that the wettability of OM, quantified by the contact angle, links the chemical structure of OM with a bundle of physical soil properties and that reduced wettability results in the stabilization of OM in soils.
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